PUE~IaZ~jMc; U! pajujld/e!onbaS layaS @ OSE$/88/E69I-OZOO

patrodal ale sapue pue sawels!p t1 aIqeJ u! palsy ale sIaiaureled D!WOJE leu!+~ .suogelnge:, 103 pasn walsh urel8old ayl ‘ [g] ~73~s kq IClleulawy pagddns alaM N pue 3 ‘d ‘13 103 asoyL =L ‘3aI uro13 H 103 pue ‘ [9] uo!slads!p sno[euIoue 103 suoyallo3 IJJ!M ‘S *Jai uIo~3 alaM ax 103 slope3 Ou!raw3s 3uro~e ua8olplCy-uou IIe 103 pa3npoIlu! SBM I(dollos!uv =suxo~e H 1~2 01 pau@sr! SCM zy 90'0 = ~ope3 am) -eladwa$ paxt3 v .Qateledas paw3al alaM pue ‘deur awala33ip Ia!Inod e uroq paup.ulalap alaM (Z)N 0~ paqDEJ$e SlUOle H OMJ aQ30 suog!sod aq& ‘(u 80’1 = H-3 ‘v S6E’ 1 = 3-D) SuIoJe uaSolpKy payawe Ijay ygM layla801 ‘saipoq p@I SE pawaIl alah SlUO)e UOqIt?a 8U!x * 1 = M lj$!M &7Mz UO!JDUn3 ay$ ou~z~w!uyl ‘salenbs-Iseal ~l~eur-Iln3 Icq paugar SBM aInwws ayL * 1.0 sEM a@3 w( ay, y ~3~!qs lalaweled ]sa%eI ay$ uayM ‘6Zo’o 30 21 xapu! luaur -aal% 1~~3 e aA@ 01 pa8laAuo3 sla$awEled p?urIaq$ pur! Ieuog!sod ‘10~~3 aIeas 30 ~uauraw3a~ .sdeur Iailnod pue uoslaued y%nolyl poqlaw uIoy+hay aql Aq paAa!yDe set arnlanlls ayl 30 uoyyos

-Juno:, U!~J!M ~ue~suo:, alaM hjjw!po!Iad palnseatu suo!xaual plepue~s OMJ, . [p] uoydIosqe 103 pue d? 103 papalroD alaM wep ayL ‘(&DE ueyl IawaI8 sag!suaw! %.t!~e~ punol8yaeq ahoqe 41e~~3y8~s alaM ya!y~ 30 E I Lp ‘suo!xaUaI anb!un p9pS BI.upla!~ ‘,sz pue .z uaawq ,_U!UI J 30 paads ue3s e ~J!M ‘poq$auI QZ-0 ayl dq paInseauI ala& sa!ilsualuI

'9ZL= (ooob 'p-m3 9P =@?I ob0-f ‘gr LO1 L'O=@,B om .E3 8 LS’I = “a ‘Z = 2 ‘&’ 9SSI =/I ‘,(E)L9’POI = k ‘(Eh9’S8 = d ‘(E)ZSSS = 2) ‘v (S)990’01 = 3 ‘(S)L16’11 = 9 ‘(S)S 1 S’E 1 = v ‘1~ dnoI8 aaeds ‘yn~a -II) ‘L’SEL = m ‘axzNE13’EHa3 :VJVp /VJSh,‘J

.sWg$as a@e-wn!paur SZ 30 TuauIaw3al salenbs -Isea Icq paytulalap alaM suo!suawp !!a3 *uog -e!psr lox ON pue low~o~y~ouou~ agydel% e YI!M la~aLuoQel33~p sdgqd e uo apeuI SE?M UogDaIIoa alea 5ag!sualul 30 luatualnseaw ayl 103 paIDalas SBM uu.u Z.0 uolsuauup unu.u~xeuI 30 le~sh3 v

epa h-x

*xaIduIoa Iellnau p2lpayel30 aleu!pIooD-x!s e I_I[ uo! (#In!uayl awes ag 0~ papuoq an ywq aI!vM N-oJ JO asoy ww ZHN-OJ, IO sla)auIeIed IwyawoaO ay$ aledruo3 01 &unyoddo ayl say8 snyl punoduro:, ayL *sua8 -01pQ auym 0~) 30 awasald ayl surn3uo3 ‘OM$ Alis -uayI! aAgeIa1 ql!M ‘~9’ I g ‘03 le a3ueuosaI peolq aqJ ‘X!S &!SUa$U! aA!J?IaI qJ!M ‘EI’Z pile 91’Z 9 )e sdnol% j1CyJaur ]uaIeA!nba-uou ayl 01 anp s$a@u!s leau hah 0~1 soys (E13a3) urnlpads XwN ayL

‘passarppe aq p~noqs a3uapuodsaIIoD UIO~M 01 sloytny,

*sdnor8 IkIol-d 0~1 ayJ30 s%!l Ihaqd aqJ30 suoy?Iqy 01 paleIa1 ale r-w 028 put? 0~8 )e &sualu! yearn-uuupaur 30 spueq Ieau 0~1

a1w ‘ I_w3 OOZE pue OOEE 1~ sanIeh (HN)(I s~ov pue8g au!ureoue%o ayJ *luasqe MOU s! huanbaq 8uy3lal4s oEax ay* seaiayM ‘I_w3 0601 lnoqe le pueq auydsoyd ayl smogs ucnIJ3ads ~1 ayL

w$Dads ~KN HI pur! ~1 ‘s~s@ue Ie$uauraja 30 s!seq atjl uo panlapeley3 seM auolaae/ZI3ZH3 ~1013 pazgIels& xaIduIo:, ayL *lapMOd uaarS!

e se PIa!A rood u! [E~dd(o~zHN)E13(o~NN)a~] xaIduro3 (A)uIn!uayI au!ure ‘op!ur! pax!ur ayl aA!% 01 (@Hy)aW-d = 01) OSNOL 30 ssa3xa ue yl!M

(y z) alnwadural xnUaI le auanIo$ snolpdyue-uou

u! sl=aI [EYdd{S-(SHz30)3=NYd~zI~Oa~] XaId -UIOD ayl leyl pun03 uaaq sey 11 spunodtuo3 asarI 30 QAFt3eal ayl30 Apnls aflw.uatsAs e 30 Iled e sv

* [g] xaIduro3 Ouye~s aqJ30 puoq xo--aa ayl OJU! put%1 ayl 30 uoglasu! 1eu1103 e 30 awanb

-asuoD e se [E~dd(S-(t10)3=N’tI)z130a~] saxaId -u103 aue$aIno!yl ay$ sap!Aold uo~l3eal ayL ‘(*H -93an-d ‘SH93 = XI) s3Na se saln3aIouI auaIpc?-0Ialay

Pl’=?MoJ (SHZ3 ‘aK = HI> [z(E~dd)zI~(~O)Oa~] 30 lno!Aeyaq aq$ pa!pn$s aM laded SnOiAald e UI

. [z] anpfsal auagu ayl 30 slosInDald se pasn aq oqe uw ou!p~ure pue op!uazey se yans spue~~~ I&E opnasd leyl u~oys aAey am I(llua3ax * [I] (auydsoyd I(leyla$ = 7 ‘ua8 -01ey = x) [ Z~Exoa~] saxaIduroa (A)u.uyuayI-oxo ayl ~11013 BU!IIEJS aIqeI!eAe ale spunoduro3 y3ns %g -uyqo 103 salnoI DgaylulCs lCueuI pue ‘pun@ se XN dnol8 opyrj ue %u!~ey saxaldwo:, Ie$atu uo~~!sue~~ 30 hrpyuaq:, ay$ u! $saIawI lualln:, yDnur s! alay

LlVlI ‘vnpvd ‘VAOpVd !p gsmt!un ‘VJ!J~~vu~ a v~gm~~o~~v~ajz.q ‘v~nmS~ou~ v+uy~ !p otuaugrvd!a

INVIZVtIE) Od-IOaOlI P=e

lap guawalaqtpvg !ap r@olowaJ a tnguy3 !p oJnJ!4sI

o.LvTIwv3 0Lmfmn

Qv21 ‘vmuag ‘mma~ !p pgsran!un ‘mpu!y3 !p owaut!imvd!a ‘VL+UC+AOUI pa a.malmN rnpug3 !p qlo~moqv7

*NO%34 ONVI3fl-I ‘ILLVMI ONVIXI(IV ‘IHXV# V3ZICINV ‘dSSOll OJaXIa8O’d

EZ SZ-EZ (8861) ZPI ‘VlW VJ!u?rYS D3!UV~OUI

sa~els uogez!p!Iqriy 1ua~a33fp ayl 01 [IaM puodsallo:,

((Z)N le O(&)E’911 ‘(1)N Je O(t)I’ILI) smole ua8 -0gu ay1 Je sa@Iv ‘(II arqe1 UT sa@Ie puoq aas) ruo]e (1)~ ay$ ~~1013 /&Me dnor8 op!unlk~e aq$ 01 S!LJ

spue%g ay1 30 ]uaLuaAoLu e ICC, paup_ura~ap IClpX!seq s! uoye~nZlgu0~ p2rpaytvo leap! ayl ~013 uoyo~ -sM -aueld s!y] o$ Jaadsal ~I!M .s[ Quo Lq pall!1

s! Bu!r aualhayd op!tu! ay] pue v 1.0 u!y$!~ JewId

-03 ale (&I ‘(z)13 ‘(1)13 ‘(1)~ ‘ax aueId aseq ayl 30 SLLIO~V .au!ydsoydphaydy pue (z)N Ieaide

pue surote 13 pue (1)~ leuo!p!.taw ~I!M p2lpaywo awufploo3-xg e s! uIop2 aa a43 1 %+J UT UMO~S sv salnaalow alalDs!p 30 sls!suoD amlxuls ayL

(P1ZLEP.O (P)O96L'O

tOI)IIO8'0 (P)SIS8'0 (P)I8P6'0 (PhT686'0 (P)6EE6'0 (E)IZZS.O WLSPP'O

(E)SPZZ'O- (E)690C'O- (L)ZZIS'O- &)9ZZP'O- wi9SP'O- WEPLE'O- (E)SSSZ'O- &)zosz'o- (E)OSZE'O-

(E)IZIE’O 0366ZZ'O (9)SLII'O (E)090Z'O WEP9Z'O W99PE'O WPOLE'O &)80PP'O WZLLE'O

ZE3 10 OE3 623 823 LZ3 923 sz3 PZ3

(pJnu~luo3)

(6)OE6E'O (E)I6LP'O (E)068S'O WSS99'0 &)OZE9'0 &)8LSP'O (0Z6ZE.O WZLLZ'O &)8ESE'O &)PZPP'O WPPES'O W919L'O (E)LEEL'O WZL09'0 (0L80S.O &)99ES'O WIE99'0 (P)6LO8'0 (P)ZL98'0 b)9P68'0 (P?LZ98'0 (Ph7E08'0 (P)O9LL'O (Sj8896.0 (P)P6OL'O (I)LPOO'I tZ)OtiS6'0 (1)6PPL'O tIKIoL~0 tZ)ZI9Z8'0

(L)ELZS'O- WESPP'O- W806P'O- W09IP'O- &)LS6Z'O- (PKPOI'O- (P)IOPI'O- (P)II61'0- (P)I9OZ'O- (t)zoLI.o- (Pk611'0- (E)ZP91'0 W8E8Z'O (E)LPZE'O (&)O~SZ'O (E)PPEI'O WS680'0 WLSEO'O- (&)ISLO'O- &hP6I'O- WEPLZ'O- &)OSEZ'O- (E)9SII'O- ts)IsLr'o- (t7!6ZZZ'O- (1)9PEO'O- (IK90E'O- tr)ss&o~o (I)9690'0-

tz)sb6EI'o-

(9jO98Z.O WIESE'C (Ej9Z6E.O (&)E9SP'O (EbO8P'O tZ)OI69'0 (ZbL89'0 (ZbZ9L'O tZ)LOt78.0 (Z)ZPPB'O (Z)E69L'O (&)9PI8'0 (E)s8s8~0 WL806'0 (E)ISI6'0 (E)ZIL8'0 (E)60Z8'0 (E&096.0 WILEO'I WZ9ZO'I (‘d98E6'0 (&)OZ98'0 M6ZL8'0 (P)66SP'O &)oowo (IKSL9'0 (1)9LZ9'0 tI)89SS.O (1)169L'O

(Z)9866S'O

EZ3 223 123 023 613 813 LID 913 SI3 PI3 EI3 213 I13 013 63 83 L3 93 S3 P3 E3 23 13

ZN IN El3 213 II3 Id

Iw

‘[~qdd(EH3”H93zHN)(EH3bH93N)E13a~] 30 aInl3n.W [Wr(O ‘I ‘%I

NZU

Inorganica Chimica Acta Letters 25

TABLE II. Bond Distances (A) and Angles (o)a

Re-Clf 1) 2.404(l) N(l)-C(19)

Re-Cl(2) 2.410(l) N(2)-C(26)

Re-Cl(3) 2.412(l) C(22)-C(23)

Re-N(1) 1.715(4) C(29)-C(30) Re-N(2) 2.214(S) P-C(l) Re-P 2.436(l) P-C(7) N(2)-H(lN) 0.98(7) P-C(13) N(2)-H(2N) 0.76(7)

1.362(6) 1.444(6)

1.536(8)

1.527(8) 1.823(4) 1.847(4) 1.825(4)

compounds with two phosphine hgands trans to one another [14, 151, confirming a structural detail already present in the molecules of ref. 10. The Re-- Cl bond distances are normal. It is noteworthy that the mean (2.409 A) of the Re-Cl bonds, which are chemically equivalent, is exactly the value found in [ReC1a(NC6Hs)(PPh3)a], where the three Cl atoms and the imido N atom are also meridional.

Cl(l)-Re-Cl(2) 167.5(l) N(l)-Re-N(2) 94.4(2)

Cl( I)-Re-Cl(3) 87.5(l) N(l)-Re-P 97.7(l)

Cl(l)-Re-N(1) 95.4(2) N(2)-Re-P 167.7(l) Cl(l)-Re-N(2) 86.9(l) Re-N(l)-C(19) 171.1(4) Cl( l)-Re-P 90.0(l) Re-N(2)-C(26) 116.3(3)

Cl(2)-Re-Cl(3) 84.0(l) Re-N(2)-H(lN) 109.0(4)

C](2)-Re-N( 1) 92.5(2) Re-N(2)-H(2N) 106.0(S)

Cl(2)-Re-N(2) 82.9(2) H(lN)-N(2)-H(2N) 115.0(7) Cl(2)-Re-P 98.6(l) C(26)-N(2)-H(lN) 102.0(4)

Cl(3)-Re-N(1) 175.1(2) C(26)-N(2)-H(2N) 108.0(S) Cl(3)-Re-N(2) 81.8(l) Re-P-C(l) 115.8(l) C](3)-Re-P 86.6( 1) Re-P-C(7) 1175(l)

Re-P-C( 13) 111.4(l)

Supplementary Material

A complete list of bond angles and distances, hydrogen positional parameters, anisotropic thermal parameters and calculated and observed structure factors can be obtained from the authors.

References

aE.s.d.s. given in parentheses refer to the last significant digit.

of the two atoms. The formal double* Re-N(1) bond (1.7 15(4) A) agrees with a mean value of 1.73 A in [ReC12(NTo)(RN=CH-C6HdO)PPha] (where R = CsH5 or CHs) [lo], with 1.726(6) A in [ReC1a(NC6HS)(PPh3)2 ] CH2C12 [I 11, and with 1.71(l) A in [ReC12(NTo)(CHOC6H40)PPh3 ] [12], whereas the Re-N(2) distance is in good agreement with previous values obtained for Re-N single bonds [13]. The C(26)-N(2) bond length is normal for aromatic C-N bonds, while the C(19)-N(1) distance (1.362(6) A), is significantly shorter, which seems to be characteristic for arylimido compounds, being observed in the above mentioned and also in other similar complexes. The Re-P bond (2.436(l) A) trans to N(2) is, as expected, shorter (by ca.

0.05 a) than the corresponding distance in

1

2

3

4

5

6 7

8

9

10

*It was proposed [9] that the Re-N bond in these com- pounds has a considerable triple-bond character.

11

12

13

14

15

W. A. Nugent and B. L. Haymore, Coord. Chem. Rev., 31, 123 (1980). R. Rossi, A. Marchi, A. Duatti, L. Magon and P. Di Bernardo, Transition Met. Chem., 10, 15 1 (1985) R. Rossi, A. Marchi, A. Duatti, L. Magon, U. Casellato and R. Graziani, J. Chem. Sot., Dalton Trans., in press. A. C. T. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr., Sect. A, 24, 35 1 (1968). ‘International Tables for X-ray Crystallography, Vol. IV, Kynoch Press, Birmingham, 1974. D. T. Cromer, Acta Crystallogr., 18. 17 (1965). R. F. Stewart, E. R. Davidson and W. T. Simpson, J. Chem. Phys., 42, 3175 (1965). G. M. Sheldrick, ‘SHELX’, program for crystal structure determination, University of Cambridge, 1975. J. Chatt, J. D. Garforth, N. P. Johnson and G. A. Rowe, J. Chem. Sot., 1012 (1964). R. Rossi, A. Marchi, A. Duatti, L Magon, U. Casellato, R. Graziani and L. Polizzotti, Inorg. Chim. Acta, 90, 121 (1984). E. Forsellini, U. Casellato, R. Graziani, M. C. Carletti and L. Magon, Acta Crystallogr., Sect. C, 40, 1795 (1984). A. Marchi, R. Rossi, A. Duatti, L. Magon, U. Casellato and R. Graziani, Transition Met. Chem., 9, 299 (1984). C. J. L. Lock and G. Turner, Acta Crystallogr., Sect. B, 11, 1764 11975); 34. 923 (1978): R. S. Shandles. R. K. Murmann and E. O..Schlemper, inorg. Chem., 13, 1373 (1974). D. Bright and J. A. Ibers, Znorg. &em., 7, 1099 (1968); 8, 703 (1969). R. J. Doedens and J. A. Ibers, Znorg. Chem., 6, 204 (1967).